CN209940847U - Phosphorus-doped self-cleaning single-silver LOW-E glass - Google Patents

Phosphorus-doped self-cleaning single-silver LOW-E glass Download PDF

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CN209940847U
CN209940847U CN201920405901.7U CN201920405901U CN209940847U CN 209940847 U CN209940847 U CN 209940847U CN 201920405901 U CN201920405901 U CN 201920405901U CN 209940847 U CN209940847 U CN 209940847U
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film layer
glass
phosphorus
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cleaning
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林改
魏佳坤
孙元平
林伟珊
翁伟林
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JIEYANG HONGGUANG COATED GLASS CO Ltd
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JIEYANG HONGGUANG COATED GLASS CO Ltd
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Abstract

The application discloses phosphorus-doped self-cleaning single-silver LOW-E glass, which is characterized in that a phosphorus-titanium dioxide composite film layer is coated on the outer side surface of a glass substrate to serve as a self-cleaning film, and a first Si layer is sequentially plated on the inner side surface of the glass substrate3N4Film layer, AZO film layer, Ag film layer, NiCr film layer, second Si3N4The film layer is used as a low-radiation composite film, can realize response in a visible light wavelength range of 380-780 nm, and improves the visible light transmittance and the sunlight transmittance so that the film layer can be used as a low-radiation composite filmThe phosphorus-doped self-cleaning single-silver LOW-E glass has an excellent energy-saving effect and a self-cleaning effect of visible light response.

Description

Phosphorus-doped self-cleaning single-silver LOW-E glass
[ technical field ] A method for producing a semiconductor device
The application belongs to the technical field of glass manufacturing, and particularly relates to phosphorus-doped self-cleaning single-silver LOW-E glass.
[ background of the invention ]
The LOW-radiation glass, also called LOW-E glass, is a glass with silver coating or fluorine-doped oxide film coated on the surface, and uses the property of the film layer reflecting far infrared ray to achieve the purposes of heat insulation and heat preservation. However, low-emissivity coated glass is difficult to be cleaned at high altitude as a glass curtain wall of a building and has certain dangerousness, so people coat nano TiO on the surface of the low-emissivity coated glass2Film of TiO2The organic matter degrading function is provided, so that the surface of the low-radiation glass has the capability of degrading organic pollutants attached to the surface of the low-radiation glass under sunlight, and organic dust attached to the surface of the low-radiation glass can be easily cleaned by water.
However, pure TiO2In the crystallization state of the film, crystal grains are in a regular tetragonal shape, show the appearance of tetragonal anatase crystals, and do not have the response of a visible light wavelength range of 380-780 nm, so that the self-cleaning effect is common, the visible light transmittance and the sunlight transmittance are reduced, and the energy-saving effect of the low-radiation glass is seriously influenced.
[ Utility model ] content
In order to solve the technical problems, the application provides the phosphorus-doped self-cleaning single-silver LOW-E glass which has a self-cleaning effect in a visible light wavelength range of 380-780 nm response, has an excellent energy-saving effect and also has a good self-cleaning effect.
In order to solve the technical problem, the following technical scheme is adopted in the application:
phosphorusDoped self-cleaning single-silver LOW-E glass comprises a first glass substrate, a second glass substrate and a hollow sealing cavity arranged between the first glass substrate and the second glass substrate, wherein the first glass substrate comprises a first glass substrate, a phosphorus-titanium dioxide composite film layer arranged on the hollow sealing cavity surface and a first Si substrate arranged on the hollow sealing cavity surface and sequentially plated on the first glass substrate3N4Film layer, AZO film layer, Ag film layer, NiCr film layer, second Si3N4And (5) film layer.
According to the phosphorus-doped self-cleaning single-silver LOW-E glass, the thickness of the phosphorus-titanium dioxide composite film layer is 90-110 nm.
The phosphorus-doped self-cleaning single-silver LOW-E glass comprises the first Si3N4The film thickness of the film layer is 20-45 nm.
The phosphorus-doped self-cleaning single-silver LOW-E glass has the Ag film layer with the thickness of 8-10 nm.
According to the phosphorus-doped self-cleaning single-silver LOW-E glass, the NiCr film is 3-5 nm thick.
A phosphorus doped self-cleaning single silver LOW-E glass as described above, said second Si3N4The film thickness is 50-85 nm.
Compared with the prior art, the beneficial effects of this application are as follows:
the utility model discloses a phosphorus doping is from clean list silver LOW-E glass, through coating phosphorus titanium dioxide composite film layer as self-cleaning clean membrane on glass substrate lateral surface, plates in proper order simultaneously on glass substrate medial surface and establishes first Si3N4Film layer, AZO film layer, Ag film layer, NiCr film layer, second Si3N4The film layer is used as a LOW-radiation composite film, response in a visible light wavelength range of 380-780 nm can be realized, the visible light transmittance and the sunlight transmittance are improved, and the phosphorus-doped self-cleaning single-silver LOW-E glass has an excellent energy-saving effect and a self-cleaning effect of visible light response; the test results of the examples of the application show that the phosphorus-doped TiO can be used for preparing the material2The visible light transmittance of the prepared low-emissivity glass is more than 68 percent, and the infrared transmittance is less than 19Percentage and heat transfer coefficient less than 1.68[ W/(+) Square meter K)]The sun-shading coefficient is less than 0.48 and the radiance is less than 0.086, and the detection result is superior to that of pure TiO2The prepared low-radiation glass has the characteristics of high visible light transmittance, low radiance, low infrared transmittance, low heat transfer coefficient and low shading coefficient, allows visible light to well penetrate through the glass and transmit the glass indoors, enhances the lighting effect, simultaneously blocks far infrared heat radiation from outdoors, plays a role in heat preservation, saves resources, saves energy and protects the environment; the hydrophilicity is an important index of the self-cleaning glass, the quality of the self-cleaning effect can be visually reflected through the contact angle, and the phosphorus-doped TiO is used2The contact angle of the prepared low-radiation glass is less than 4.9 degrees, and the prepared low-radiation glass is pure TiO2The contact angle of the prepared low-radiation glass is 8.4 degrees and 8.6 degrees, so that the self-cleaning glass has a better self-cleaning effect, has a self-cleaning effect in a visible light wavelength range of 380-780 nm response, can reduce the cleaning times of curtain wall glass, and has a wide application scene in glass curtain walls and building doors and windows.
[ description of the drawings ]
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings used in the description of the embodiments will be briefly introduced below.
FIG. 1 is a schematic structural view of a phosphorus-doped self-cleaning single silver LOW-E glass of the present invention.
[ detailed description ] embodiments
The phosphorus-doped self-cleaning single-silver LOW-E glass as shown in FIG. 1 comprises a first glass substrate 1, a second glass substrate 2 and a hollow sealed cavity 3 arranged between the first glass substrate and the second glass substrate. The first glass substrate 1 comprises a first glass substrate 11, a phosphorus-titanium dioxide composite film layer 12 arranged on the surface of the hollow sealed cavity 3 far away from the first glass substrate 11 and a first Si sequentially plated on the surface of the hollow sealed cavity 3 close to the first glass substrate 113N4Film layer 13, AZO film layer 14, Ag film layer 15, NiCr film layer 16 and second Si3N4 A membrane layer 17.
The application adopts the phosphorus-titanium dioxide composite film layer 12 coated on the outer side surface of the glass substrate 11 as a self-cleaning film,simultaneously, the first Si is plated on the inner side surface of the glass substrate 11 in sequence3N4 A film layer 13, the AZO film layer 14, the Ag film layer 15, the NiCr film layer 16, and the second Si3N4The film layer 17 is used as a LOW-radiation composite film, can realize response in a visible light wavelength range of 380-780 nm, and improves the visible light transmittance and sunlight transmittance, so that the phosphorus-doped self-cleaning single-silver LOW-E glass has an excellent energy-saving effect and a self-cleaning effect of visible light response. The phosphorus-doped self-cleaning single-silver LOW-E glass has the characteristics of high visible light transmittance, LOW radiance, LOW infrared transmittance, LOW heat transfer coefficient and LOW shading coefficient, allows visible light to well penetrate through the glass and transmits the glass into a room, enhances the lighting effect, simultaneously blocks far infrared heat radiation from the outside, has the self-cleaning effect in the response of the visible light wavelength range of 380-780 nm, and can reduce the cleaning times of curtain wall glass.
The thickness of the phosphorus-titanium dioxide composite film layer 12 is 90-110 nm, and 5% of phosphorus-doped TiO is coated by a roll coating method2The solution is then tempered to obtain the 5 percent of the phosphorus-doped TiO2The solution is prepared by using 30-100 ml of tetrabutyl titanate as a precursor, 190-210 ml of absolute ethyl alcohol and 20-30 ml of H2O230-50 ml of deionized water as solvent, 10-20 ml of acetylacetone as chelating agent, and 20-30 ml of HNO3As a catalyst, adding 6-20 ml of H3PO4And (4) preparing. Due to pure TiO2In the crystallization state of the film, crystal grains are in a regular tetragonal shape, show the shape of tetragonal anatase crystals, and do not have the response of 380-780 nm in the visible wavelength range, and the phosphorus-titanium dioxide composite film layer 12 is optimally prepared to obtain phosphorus-doped TiO2Film of TiO, film of2The crystal shape of the film is obviously changed, the anatase crystal form in cylindrical oriented distribution can appear, the response in the visible light wavelength range of 380-780 nm can be realized, the visible light transmittance and the sunlight transmittance are improved, and the phosphorus-doped self-cleaning single-silver LOW-E glass has an excellent energy-saving effect and a self-cleaning effect of visible light response. The phosphorus titanium dioxide composite thin film layer 12 of the present application has super-hydrophilicity, and the hydrophilicity isThe phosphorus-doped self-cleaning single-silver LOW-E glass is an important index of self-cleaning effect, and water can be easily spread on the surface by means of the hydrophilic characteristic, so that inorganic matters such as dust and the like adsorbed on the surface of the glass can be easily washed away, and the self-cleaning glass can be kept clean for a long time by natural rainwater under normal conditions.
The first Si3N4The film 13 has a thickness of 20-45 nm and is formed by magnetron sputtering a silicon-aluminum target Si, Al 92:8 (wt%), sputtering with an AC power source, and Ar, N2As sputtering gas, Ar, N2Gas flow 400SCCM 600 SCCM. The first Si3N4The film layer 13 is used as a first medium film layer, has high firmness, improves the adhesive force of the LOW-radiation film 13 and the first glass substrate 11, has high reflectivity to infrared rays, and can increase the reflectivity of the phosphorus-doped self-cleaning single-silver LOW-E glass to infrared bands.
The thickness of the AZO film layer 14 is 300-500 nm, and the AZO film layer is formed by magnetron sputtering aluminum-doped zinc oxide target ZnO, Al is 92:8 (wt%), sputtering is carried out by using an alternating current power supply, and Ar and O are used2Gas flow 1000SCCM 40 SCCM. The AZO film layer 14 is an aluminum-doped zinc oxide film and has the function of reducing infrared transmittance.
The Ag film layer 15 is 8-10 nm thick and is formed by magnetron sputtering of the Ag film layer, direct-current power sputtering is carried out, Ar is used as sputtering gas, and the gas flow is 500-550 SCCM. The Ag film layer 15 serves as a functional film layer, and functions to reflect infrared rays and simultaneously reduce destructive ultraviolet rays in sunlight from entering the room.
The NiCr film layer 16 is 3-5 nm thick and is a magnetron sputtering NiCr film layer, the NiCr film layer is sputtered by a direct current power supply, Ar is used as sputtering gas, and the gas flow is 500-550 SCCM. The NiCr film layer is used as a shielding film layer and is used for preventing the Ag film layer 15 from being oxidized to lose the low-radiation function.
The second Si3N4The film 17 has a thickness of 50-85 nm and is formed by magnetron sputtering a silicon-aluminum target Si, Al 92:8 (wt%), sputtering with an AC power source, and Ar, N2As sputtering gas, Ar, N2Gas flow 400SCCM 600 SCCM. As an outer film medium film, the film is used for infrared rayHas high reflectivity, while the Si3N4The film layer 17 has good hardness, can well protect the Ag film layer 15, and improves the physical and chemical properties of the phosphorus-doped self-cleaning single-silver LOW-E glass.
The first glass substrate 11 and the second glass substrate 2 are both made of float glass with the thickness of 4-10 mm, and the float glass is used as the glass substrate and has good light transmission and lighting performance. Through will first glass substrate 11 with second glass substrate 2 processing synthesizes into cavity glass, will phosphorus titanium dioxide composite film layer 12 coats first glass substrate 11 lateral surface, low-emissivity composite film 13 plates and establishes on first glass substrate 11 towards the surface in cavity sealed chamber 3, protect low-emissivity composite film 13, prevent to oxidize and destroy, cavity glass itself just has energy-conserving effect, has added the energy-conserving effect of low-emissivity film, can make whole building glass's energy-conserving effect better, on the other hand can utilize cavity glass sound insulation performance, noise pollution abatement.
This application is through coating on 11 lateral surfaces of glass substrate phosphorus titanium dioxide composite film layer 12 establishes as self-cleaning membrane, plates in proper order simultaneously on 11 medial surfaces of glass substrate first Si3N4A film layer 13, the AZO film layer 14, the Ag film layer 15, the NiCr film layer 16, and the second Si3N4The film layer 17 is used as a LOW-radiation composite film, can realize response in a visible light wavelength range of 380-780 nm, and improves the visible light transmittance and sunlight transmittance, so that the phosphorus-doped self-cleaning single-silver LOW-E glass has an excellent energy-saving effect and a self-cleaning effect of visible light response.
The preparation method of the phosphorus-doped self-cleaning single silver LOW-E glass is further described with reference to specific examples 1-6 as follows:
example 1:
the preparation method of the phosphorus-doped self-cleaning single-silver LOW-E glass comprises the following steps:
A. coating a phosphorus titanium dioxide composite film layer: using a roll coating method to dope 5% of phosphorus-doped TiO2The solution was applied to either side surface of a first glass substrate having a thickness of 6mmCoating a phosphorus-titanium dioxide composite film layer with the thickness of 100nm, and then putting the coated film layer into a toughening furnace for toughening to obtain toughened self-cleaning glass;
B. cleaning the uncoated surface of the self-cleaning glass, and sending the cleaned surface into a magnetron sputtering plating machine for magnetron sputtering layer by layer;
C. plating first Si3N4Film layer: sputtering with AC power, Ar, N2As sputtering gas, silicon aluminum target Si, Al 92:8 (wt%), Ar, N were magnetron sputtered2Gas flow 400SCCM, 600SCCM, magnetron sputtering first Si with film thickness of 30nm3N4A film layer;
D. plating an AZO film layer: sputtering with AC power, Ar, O2As sputtering gas, magnetron sputtering aluminum-doped zinc oxide target ZnO, Al 92:8 (wt%), Ar, O2The gas flow is 1000SCCM, 40SCCM, and the magnetron sputtering film thickness is an AZO film layer with 400 nm;
E. plating an Ag film layer: sputtering by using a direct current power supply, wherein Ar is used as sputtering gas, the gas flow is 500SCCM, and the magnetron sputtering film thickness is 10 nm;
F. plating a NiCr film layer: sputtering by using a direct current power supply, wherein Ar is used as sputtering gas, the gas flow is 520SCCM, and the magnetron sputtering film thickness is 4 nm;
G. plating with second Si3N4Film layer: sputtering with AC power, Ar, N2As sputtering gas, silicon aluminum target Si, Al 92:8 (wt%), Ar, N were magnetron sputtered2Gas flow 400SCCM, 600SCCM, second Si with 60nm magnetron sputtering film thickness3N4Obtaining a single-layer phosphorus-doped self-cleaning single-silver LOW-E glass;
H. processing and synthesizing: the single-layer phosphorus-doped self-cleaning single-silver LOW-E glass is plated with the first Si3N4A film layer, the AZO film layer, the Ag film layer, the NiCr film layer, and the second Si3N4And separating one surface of the film layer and a second glass substrate with the thickness of 6mm to form a hollow sealed cavity, and processing and synthesizing to obtain the hollow glass.
The 5% of the phosphorus-doped TiO in the step A2The preparation method of the solution comprises the following steps：
a. 70ml of tetrabutyl titanate is dissolved in 200ml of absolute ethyl alcohol and 25ml of H2O2Stirring for 30min, and dripping 40ml of deionized water while stirring to obtain a first mixed solution;
b. adding 15ml of acetylacetone and 25ml of HNO into the first mixed solution3Heating to 40 ℃, and stirring for 30min to obtain a second mixed solution;
c. 14ml of H was added dropwise to the second mixed solution3PO4Heating to 80 ℃, and stirring for 2.0h to obtain a third mixed solution;
d. and (3) putting the third mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, heating to 135 ℃, stirring for 2.0h under the pressure of 4bar, and filtering to obtain the polytetrafluoroethylene-containing composite material.
Example 2:
the preparation method of the phosphorus-doped self-cleaning single-silver LOW-E glass comprises the following steps:
A. coating a phosphorus titanium dioxide composite film layer: using a roll coating method to dope 5% of phosphorus-doped TiO2Coating the solution on any side surface of a first glass substrate with the thickness of 4mm, coating a phosphorus-titanium dioxide composite film layer with the film thickness of 110nm, and placing the coated film layer into a toughening furnace for toughening to obtain toughened self-cleaning glass;
B. cleaning the uncoated surface of the self-cleaning glass, and sending the cleaned surface into a magnetron sputtering plating machine for magnetron sputtering layer by layer;
C. plating first Si3N4Film layer: sputtering with AC power, Ar, N2As sputtering gas, silicon aluminum target Si, Al 92:8 (wt%), Ar, N were magnetron sputtered2Gas flow 400SCCM, 600SCCM, magnetron sputtering first Si with film thickness of 25nm3N4A film layer;
D. plating an AZO film layer: sputtering with AC power, Ar, O2As sputtering gas, magnetron sputtering aluminum-doped zinc oxide target ZnO, Al 92:8 (wt%), Ar, O2The gas flow is 1000SCCM, 40SCCM, and the magnetron sputtering film thickness is 300nm of AZO film layer;
E. plating an Ag film layer: sputtering by using a direct current power supply, wherein Ar is used as sputtering gas, the gas flow rate is 530SCCM, and the magnetron sputtering film thickness is 10 nm;
F. plating a NiCr film layer: sputtering by using a direct current power supply, wherein Ar is used as sputtering gas, the gas flow is 510SCCM, and the magnetron sputtering film thickness is a NiCr film layer with the thickness of 3 nm;
G. plating with second Si3N4Film layer: sputtering with AC power, Ar, N2As sputtering gas, silicon aluminum target Si, Al 92:8 (wt%), Ar, N were magnetron sputtered2Gas flow 400SCCM, 600SCCM, second Si with magnetron sputtering film thickness of 80nm3N4Obtaining a single-layer phosphorus-doped self-cleaning single-silver LOW-E glass;
H. processing and synthesizing: the single-layer phosphorus-doped self-cleaning single-silver LOW-E glass is plated with the first Si3N4A film layer, the AZO film layer, the Ag film layer, the NiCr film layer, and the second Si3N4And separating one surface of the film layer and a second glass substrate with the thickness of 8mm to form a hollow sealed cavity, and processing and synthesizing to obtain the hollow glass.
The 5% of the phosphorus-doped TiO in the step A2The preparation method of the solution comprises the following steps:
a. 85ml of tetrabutyl titanate is dissolved in 195ml of absolute ethanol and 20ml of H2O2Stirring for 35min, and dripping 50ml of deionized water while stirring to obtain a first mixed solution;
b. 10ml of acetylacetone and 30ml of HNO were added to the first mixed solution3Heating to 30 ℃, and stirring for 40min to obtain a second mixed solution;
c. 8ml of H was added dropwise to the second mixed solution3PO4Heating to 90 ℃, and stirring for 2.2 hours to obtain a third mixed solution;
d. and (3) putting the third mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, heating to 133 ℃, stirring for 2.0h under the pressure of 3bar, and filtering to obtain the polytetrafluoroethylene-containing composite material.
Example 3:
the preparation method of the phosphorus-doped self-cleaning single-silver LOW-E glass comprises the following steps:
A. phosphorus-coated titanium dioxide composite filmLayer (b): using a roll coating method to dope 5% of phosphorus-doped TiO2Coating the solution on any side surface of a first glass substrate with the thickness of 10mm, coating a phosphorus-titanium dioxide composite film layer with the film thickness of 90nm, and placing the coated film layer into a toughening furnace for toughening to obtain toughened self-cleaning glass;
B. cleaning the uncoated surface of the self-cleaning glass, and sending the cleaned surface into a magnetron sputtering plating machine for magnetron sputtering layer by layer;
C. plating first Si3N4Film layer: sputtering with AC power, Ar, N2As sputtering gas, silicon aluminum target Si, Al 92:8 (wt%), Ar, N were magnetron sputtered2Gas flow 400SCCM, 600SCCM, first Si with magnetron sputtering film thickness of 45nm3N4A film layer;
D. plating an AZO film layer: sputtering with AC power, Ar, O2As sputtering gas, magnetron sputtering aluminum-doped zinc oxide target ZnO, Al 92:8 (wt%), Ar, O2The gas flow is 1000SCCM, 40SCCM, and the magnetron sputtering film thickness is 500nm AZO film layer;
E. plating an Ag film layer: sputtering by using a direct current power supply, wherein Ar is used as sputtering gas, the gas flow is 510SCCM, and the magnetron sputtering film thickness is 8 nm;
F. plating a NiCr film layer: sputtering by using a direct current power supply, wherein Ar is used as sputtering gas, the gas flow is 550SCCM, and the magnetron sputtering film thickness is a NiCr film layer with 3.5 nm;
G. plating with second Si3N4Film layer: sputtering with AC power, Ar, N2As sputtering gas, silicon aluminum target Si, Al 92:8 (wt%), Ar, N were magnetron sputtered2Gas flow 400SCCM, 600SCCM, magnetron sputtering second Si with film thickness of 75nm3N4Obtaining a single-layer phosphorus-doped self-cleaning single-silver LOW-E glass;
H. processing and synthesizing: the single-layer phosphorus-doped self-cleaning single-silver LOW-E glass is plated with the first Si3N4A film layer, the AZO film layer, the Ag film layer, the NiCr film layer, and the second Si3N4And separating one surface of the film layer and a second glass substrate with the thickness of 6mm to form a hollow sealed cavity, and processing and synthesizing to obtain the hollow glass.
The 5% of the phosphorus-doped TiO in the step A2The preparation method of the solution comprises the following steps:
a. dissolving 100ml of tetrabutyl titanate in 190ml of absolute ethyl alcohol and 30ml of H2O2Stirring for 40min, and dripping 35ml of deionized water while stirring to obtain a first mixed solution;
b. 12ml of acetylacetone and 28ml of HNO were added to the first mixed solution3Heating to 35 ℃, and stirring for 35min to obtain a second mixed solution;
c. 18ml of H was added dropwise to the second mixed solution3PO4Heating to 85 ℃, and stirring for 2.5 hours to obtain a third mixed solution;
d. and (3) putting the third mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, heating to 130 ℃, stirring for 1.5h under the pressure of 3.5bar, and filtering to obtain the polytetrafluoroethylene-containing composite material.
Example 4:
the preparation method of the phosphorus-doped self-cleaning single-silver LOW-E glass comprises the following steps:
A. coating a phosphorus titanium dioxide composite film layer: using a roll coating method to dope 5% of phosphorus-doped TiO2Coating the solution on any side surface of a first glass substrate with the thickness of 6mm, coating a phosphorus-titanium dioxide composite film layer with the film thickness of 105nm, and placing the coated film layer into a toughening furnace for toughening to obtain toughened self-cleaning glass;
B. cleaning the uncoated surface of the self-cleaning glass, and sending the cleaned surface into a magnetron sputtering plating machine for magnetron sputtering layer by layer;
C. plating first Si3N4Film layer: sputtering with AC power, Ar, N2As sputtering gas, silicon aluminum target Si, Al 92:8 (wt%), Ar, N were magnetron sputtered2Gas flow 400SCCM, 600SCCM, first Si with 40nm magnetron sputtering film thickness3N4A film layer;
D. plating an AZO film layer: sputtering with AC power, Ar, O2As sputtering gas, magnetron sputtering aluminum-doped zinc oxide target ZnO, Al 92:8 (wt%), Ar, O2The gas flow is 1000SCCM, 40SCCM, and the magnetron sputtering film thickness is 350nm of AZO film layer;
E. plating an Ag film layer: sputtering by using a direct current power supply, wherein Ar is used as sputtering gas, the gas flow is 550SCCM, and the magnetron sputtering film thickness is 9 nm;
F. plating a NiCr film layer: sputtering by using a direct current power supply, wherein Ar is used as sputtering gas, the gas flow rate is 530SCCM, and the magnetron sputtering film thickness is a NiCr film layer with 4.5 nm;
G. plating with second Si3N4Film layer: sputtering with AC power, Ar, N2As sputtering gas, silicon aluminum target Si, Al 92:8 (wt%), Ar, N were magnetron sputtered2Gas flow 400SCCM, 600SCCM, magnetron sputtering film thickness 85nm second Si3N4Obtaining a single-layer phosphorus-doped self-cleaning single-silver LOW-E glass;
H. processing and synthesizing: the single-layer phosphorus-doped self-cleaning single-silver LOW-E glass is plated with the first Si3N4A film layer, the AZO film layer, the Ag film layer, the NiCr film layer, and the second Si3N4And separating one surface of the film layer and a second glass substrate with the thickness of 4mm to form a hollow sealed cavity, and processing and synthesizing to obtain the hollow glass.
The 5% of the phosphorus-doped TiO in the step A2The preparation method of the solution comprises the following steps:
a. dissolving 30ml of tetrabutyl titanate in 250ml of absolute ethyl alcohol and 28ml of H2O2Stirring for 20min, and dripping 30ml of deionized water while stirring to obtain a first mixed solution;
b. 18ml of acetylacetone and 22ml of HNO were added to the first mixed solution3Heating to 45 ℃, and stirring for 20min to obtain a second mixed solution;
c. 20ml of H was added dropwise to the second mixed solution3PO4Heating to 80 ℃, and stirring for 1.8h to obtain a third mixed solution;
d. and (3) putting the third mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, heating to 138 ℃, stirring for 2.5 hours at the pressure of 3bar, and filtering to obtain the polytetrafluoroethylene-containing composite material.
Example 5:
the preparation method of the phosphorus-doped self-cleaning single-silver LOW-E glass comprises the following steps:
A. coating a phosphorus titanium dioxide composite film layer: using a roll coating method to dope 5% of phosphorus-doped TiO2Coating the solution on any side surface of a first glass substrate with the thickness of 8mm, coating a phosphorus-titanium dioxide composite film layer with the film thickness of 95nm, and placing the coated film layer into a toughening furnace for toughening to obtain toughened self-cleaning glass;
B. cleaning the uncoated surface of the self-cleaning glass, and sending the cleaned surface into a magnetron sputtering plating machine for magnetron sputtering layer by layer;
C. plating first Si3N4Film layer: sputtering with AC power, Ar, N2As sputtering gas, silicon aluminum target Si, Al 92:8 (wt%), Ar, N were magnetron sputtered2Gas flow 400SCCM, 600SCCM, magnetron sputtering first Si with film thickness of 20nm3N4A film layer;
D. plating an AZO film layer: sputtering with AC power, Ar, O2As sputtering gas, magnetron sputtering aluminum-doped zinc oxide target ZnO, Al 92:8 (wt%), Ar, O2The gas flow is 1000SCCM, 40SCCM, and the magnetron sputtering film thickness is an AZO film layer with 400 nm;
E. plating an Ag film layer: sputtering by using a direct current power supply, wherein Ar is used as sputtering gas, the gas flow is 540SCCM, and the magnetron sputtering film thickness is 8.5 nm;
F. plating a NiCr film layer: sputtering by using a direct current power supply, wherein Ar is used as sputtering gas, the gas flow is 500SCCM, and the magnetron sputtering film thickness is a NiCr film layer with 5 nm;
G. plating with second Si3N4Film layer: sputtering with AC power, Ar, N2As sputtering gas, silicon aluminum target Si, Al 92:8 (wt%), Ar, N were magnetron sputtered2Gas flow 400SCCM, 600SCCM, second Si with magnetron sputtering film thickness of 50nm3N4Obtaining a single-layer phosphorus-doped self-cleaning single-silver LOW-E glass;
H. processing and synthesizing: the single-layer phosphorus-doped self-cleaning single-silver LOW-E glass is plated with the first Si3N4A film layer, the AZO film layer, the Ag film layer, the NiCr film layer, and the second Si3N4One side of the film layerAnd separating the second glass substrate with the thickness of 10mm to form a hollow sealed cavity, and processing and synthesizing the second glass substrate to obtain the hollow glass.
The 5% of the phosphorus-doped TiO in the step A2The preparation method of the solution comprises the following steps:
a. dissolving 55ml of tetrabutyl titanate in 200ml of absolute ethyl alcohol and 26ml of H2O2Stirring for 25min, and dripping 40ml of deionized water while stirring to obtain a first mixed solution;
b. 16ml of acetylacetone and 20ml of HNO were added to the first mixed solution3Heating to 48 ℃, and stirring for 28min to obtain a second mixed solution;
c. 12ml of H was added dropwise to the second mixed solution3PO4Heating to 75 ℃, and stirring for 1.5h to obtain a third mixed solution;
d. and (3) putting the third mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, heating to 140 ℃, stirring for 1.8 hours at the pressure of 4bar, and filtering to obtain the polytetrafluoroethylene-containing composite material.
Example 6:
the preparation method of the phosphorus-doped self-cleaning single-silver LOW-E glass comprises the following steps:
A. coating a phosphorus titanium dioxide composite film layer: using a roll coating method to dope 5% of phosphorus-doped TiO2Coating the solution on any side surface of a first glass substrate with the thickness of 8mm, coating a phosphorus-titanium dioxide composite film layer with the film thickness of 100nm, and placing the coated film layer into a toughening furnace for toughening to obtain toughened self-cleaning glass;
B. cleaning the uncoated surface of the self-cleaning glass, and sending the cleaned surface into a magnetron sputtering plating machine for magnetron sputtering layer by layer;
C. plating first Si3N4Film layer: sputtering with AC power, Ar, N2As sputtering gas, silicon aluminum target Si, Al 92:8 (wt%), Ar, N were magnetron sputtered2Gas flow 400SCCM, 600SCCM, first Si with 35nm of magnetron sputtering film thickness3N4A film layer;
D. plating an AZO film layer: sputtering with AC power, Ar, O2As sputtering gas, magnetron sputtering aluminum-doped oxideZinc target ZnO Al 92:8 (wt%), Ar, O2The gas flow is 1000SCCM, 40SCCM, and the magnetron sputtering film thickness is AZO film layer of 450 nm;
E. plating an Ag film layer: sputtering by using a direct current power supply, wherein Ar is used as sputtering gas, the gas flow is 520SCCM, and the magnetron sputtering film thickness is 9.5 nm;
F. plating a NiCr film layer: sputtering by using a direct current power supply, wherein Ar is used as sputtering gas, the gas flow is 540SCCM, and the magnetron sputtering film thickness is a NiCr film layer with 4 nm;
G. plating with second Si3N4Film layer: sputtering with AC power, Ar, N2As sputtering gas, silicon aluminum target Si, Al 92:8 (wt%), Ar, N were magnetron sputtered2Gas flow 400SCCM, 600SCCM, second Si with 70nm magnetron sputtering film thickness3N4Obtaining a single-layer phosphorus-doped self-cleaning single-silver LOW-E glass;
H. processing and synthesizing: the single-layer phosphorus-doped self-cleaning single-silver LOW-E glass is plated with the first Si3N4A film layer, the AZO film layer, the Ag film layer, the NiCr film layer, and the second Si3N4And separating one surface of the film layer and a second glass substrate with the thickness of 8mm to form a hollow sealed cavity, and processing and synthesizing to obtain the hollow glass.
The 5% of the phosphorus-doped TiO in the step A2The preparation method of the solution comprises the following steps:
a. 40ml of tetrabutyl titanate are dissolved in 210ml of absolute ethanol and 22ml of H2O2Stirring for 30min, and dripping 45ml of deionized water while stirring to obtain a first mixed solution;
b. adding 20ml of acetylacetone and 24ml of HNO into the first mixed solution3Heating to 50 ℃, and stirring for 25min to obtain a second mixed solution;
c. 6ml of H was added dropwise to the second mixed solution3PO4Heating to 70 ℃, and stirring for 2.4 hours to obtain a third mixed solution;
d. and (3) putting the third mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, heating to 136 ℃, stirring for 2.2 hours under the pressure of 3.5bar, and filtering to obtain the polytetrafluoroethylene-containing composite material.
Comparative example 1
The procedure of the preparation method is the same as that of example 1, but pure TiO undoped with phosphorus is used2The solution replaces 5 percent of the phosphorus-doped TiO in the step A2Solution to coat pure TiO2A thin film layer.
Comparative example 2
The same procedure as in example 3 was followed, but using pure TiO undoped with phosphorus2The solution replaces 5 percent of the phosphorus-doped TiO in the step A2Solution to coat pure TiO2A thin film layer.
Table 1: film compositions of examples 1-6 and comparative examples 1-2
Figure BDA0002008761070000181
Table 2: examples 1-6 step A5% phosphorus-doped TiO2Proportioning of the solution
Figure BDA0002008761070000191
The products prepared in examples 1-6 and comparative examples 1-2 were tested for visible light transmittance, infrared transmittance, heat transfer coefficient, solar shading coefficient, and radiance optical performance, respectively, and contact angle, and the test results are shown in table 3.
The contact angle measuring method comprises the following steps:
a. washing a sample to be tested with distilled water, absolute ethyl alcohol, acetone and distilled water in sequence, and drying;
b. placing a sample to be detected into a photoreactor to irradiate for 1 h;
c. the sample to be tested is taken out and placed on a contact angle tester (Zhijia ZJIA, ZJ-SDC-200) to test the contact angle of the sample to water.
Table 3: results of Performance test of examples 1 to 6 and comparative examples 1 to 2
Figure BDA0002008761070000192
Figure BDA0002008761070000201
As shown in the test results in Table 3, the visible light transmittance > 68% of the low-emissivity glass prepared in the examples of the present application is higher than that of the low-emissivity glass prepared in the comparative examples 1-6 than that of the low-emissivity glass prepared in the comparative examples 1-2, and the pure TiO of the comparative examples2The prepared low radiation glass is 45% and 52% respectively, which shows that the application has higher visible light transmittance, and simultaneously, in the test result of the application, the infrared transmittance is less than 19%, and the heat transfer coefficient is less than 1.68[ W/(. square meter. K)]The solar shading coefficient is less than 0.48 and the radiance is less than 0.086, the solar shading coefficient is superior to test data of a comparative example, the solar shading coefficient has the characteristics of high visible light transmittance, low radiance, low infrared transmittance, low heat transfer coefficient and low solar shading coefficient, visible light is allowed to well penetrate through the glass and is transmitted into the room, the lighting effect is enhanced, and far infrared heat radiation from the outside is blocked.
The hydrophilicity is an important index of the self-cleaning glass, which is generally expressed by a contact angle, the quality of the self-cleaning effect can be visually reflected by the contact angle, and the experimental result shown in the table 3 shows that the phosphorus-doped TiO is doped in the self-cleaning glass2The contact angle of the prepared low-radiation glass is less than 4.9 degrees, and the prepared low-radiation glass is pure TiO2The contact angles of the prepared low-emissivity glass are 8.4 degrees and 8.6 degrees. Therefore, the curtain wall glass cleaning device has a better self-cleaning effect, has a self-cleaning effect in a visible light wavelength range of 380-780 nm response, and can reduce the cleaning times of the curtain wall glass.

Claims (8)

1. The utility model provides a phosphorus doping is from clean list silver LOW-E glass, includes first glass substrate (1), second glass base member (2) and locates cavity seal chamber (3) between the two, its characterized in that: the first glass substrate (1) comprises a first glass substrate (11), a phosphorus-titanium dioxide composite film layer (12) arranged on the surface of the hollow sealed cavity (3) and a first glass substrate (11) sequentially plated on the surface of the hollow sealed cavity (3)First Si of3N4A film layer (13), an AZO film layer (14), an Ag film layer (15), a NiCr film layer (16), and a second Si3N4A membrane layer (17).
2. The phosphorus-doped self-cleaning single silver LOW-E glass according to claim 1, wherein: the thickness of the phosphorus-titanium dioxide composite film layer (12) is 90-110 nm.
3. The phosphorus-doped self-cleaning single silver LOW-E glass according to claim 1, wherein: the first Si3N4The film thickness of the film layer (13) is 20-45 nm.
4. The phosphorus-doped self-cleaning single silver LOW-E glass according to claim 1, wherein: the thickness of the AZO film layer (14) is 300-500 nm.
5. The phosphorus-doped self-cleaning single silver LOW-E glass according to claim 1, wherein: the Ag film layer (15) is 8-10 nm thick.
6. The phosphorus-doped self-cleaning single silver LOW-E glass according to claim 1, wherein: the NiCr film layer (16) is 3-5 nm thick.
7. The phosphorus-doped self-cleaning single silver LOW-E glass according to claim 1, wherein: the second Si3N4The film thickness of the film layer (17) is 50-85 nm.
8. The phosphorus-doped self-cleaning single silver LOW-E glass according to claim 1, wherein: the first glass substrate (11) and the second glass substrate (2) are both made of float glass with the thickness of 4-10 mm.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109824276A (en) * 2019-03-27 2019-05-31 揭阳市宏光镀膜玻璃有限公司 A kind of phosphorus doping self-cleaning list silver LOW-E glass and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109824276A (en) * 2019-03-27 2019-05-31 揭阳市宏光镀膜玻璃有限公司 A kind of phosphorus doping self-cleaning list silver LOW-E glass and preparation method thereof

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